CN103137961B - Positive electrode and preparation method thereof and comprise the lithium ion battery of this positive electrode - Google Patents
Positive electrode and preparation method thereof and comprise the lithium ion battery of this positive electrode Download PDFInfo
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- CN103137961B CN103137961B CN201210250864.XA CN201210250864A CN103137961B CN 103137961 B CN103137961 B CN 103137961B CN 201210250864 A CN201210250864 A CN 201210250864A CN 103137961 B CN103137961 B CN 103137961B
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Abstract
The invention belongs to technical field of lithium ion, particularly relate to a kind of positive electrode, positive electrode is formed by body phase material and the skin-material being positioned at body phase material surface are melted, body phase material is cobalt acid lithium, skin-material is the melted little granule of stratiform nickel ion doped composition, and it is 0.1 ~ 10% that skin-material accounts for the mass percent of positive electrode.Relative to prior art, the positive electrode lithium ion conduction performance excellent owing to clad has that the present invention is formed at the Surface coating stratiform nickel ion doped of cobalt acid lithium, not only will not reduce the discharge voltage plateau of positive electrode, the discharge voltage plateau of this positive electrode can be improved the most to a certain extent；And this clad can also play effective gram volume under high voltages, strengthen the structural stability of matrix material, it is thus possible to significantly improve discharge capacity and the cycle life of positive electrode under high voltage.Additionally, the invention also discloses the preparation method of this positive electrode a kind of and comprise the lithium ion battery of this positive electrode.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of positive electrode and preparation method thereof and the lithium ion battery comprising this positive electrode.
Background technology
Lithium ion battery generally comprises positive plate, negative plate, the isolating membrane that is interval between positive/negative plate, and electrolyte, wherein, positive plate includes plus plate current-collecting body and the positive electrode being distributed on plus plate current-collecting body, and negative plate includes negative current collector and the negative material being distributed on negative current collector.At present, conventional lithium ion anode material is LiCoO2And LiNiCoMnO2Deng.
At present, the battery that the consumption electronic product such as mobile phone and panel computer uses gradually develops towards lightening direction, and therefore, exploitation has the positive electrode of more high-quality energy density or volume energy density becomes the focus that lithium ion battery develops.And volume energy density=(discharge capacity) × (discharge voltage plateau) × (compacted density), keeping the situation that material compacted density is constant, improve the charge cutoff voltage of positive electrode, discharge capacity and discharge voltage plateau will be improved, thus improve its energy density.
When the running voltage of full battery (negative pole is graphite) is 4.2V, LiCoO2Electric discharge gram volume is about 140mAh/g, and discharge voltage plateau is about 3.70V；And when running voltage improves to 4.3V, LiCoO2Electric discharge gram volume is about 154mAh/g, and discharge voltage plateau is about 3.72V；When running voltage improves further to 4.35V, LiCoO2Electric discharge gram volume is about 162mAh/g, and discharge voltage plateau is about 3.73V, the most often improves 0.1V, and electric discharge gram volume improves about 10%, and discharge voltage plateau improves about 0.02V.But, after blanking voltage raising (particularly more than 4.3V), LiCoO2Structural instability, can bring the series of problems such as charge and discharge cycles under high voltage is poor, high-temperature storage performance is the best.Therefore, LiCoO2The raising of blanking voltage be restricted.
In order to make LiCoO2Can use under higher charge cutoff voltage Deng positive electrode, it is necessary to be modified positive electrode processing.Lot of domestic and international document and patent report employing Al2O3、AlPO4、ZrO2And TiO2Deng metal-oxide, positive electrode carried out Surface coating, they think that Surface coating can improve the surface texture stability of positive electrode, such that it is able to improve battery cycle performance under high voltages, but actual effectiveness comparison is limited, the most also can bring counter productive: because the metal-oxide of cladding is non-electroactive materials, lead lithium ion very poor, gram volume and the discharge voltage plateau of positive electrode can be sacrificed after cladding, reduce the energy density of positive electrode to a certain extent.Along with people's deepening continuously to the research of positive electrode, it has been found that use a kind of another kind of positive electrode of positive electrode cladding can be efficiently against disadvantages mentioned above.
Such as, the Japanese patent application of Publication No. JP 2002-260659, use the spinelle LiMn doped with metal2O4Clad anode material improves its cycle performance at high temperature, i.e. Li(1+x)Mn(2-x-y)MyO4(M is Fe, Cr, Ni, Rh, Al, and 0 < x < 0.2,0 < y < 0.2).But in charge and discharge process, the valence state of Mn is valency change from+3 to+4, is easily generated Jahn-Teller effect, distortion of lattice, volume contraction or expansion occurring, structure becomes unstable and subsides；At high temperature, especially in high voltage system, in electrolyte, the HF of trace can cause Mn2+Dissolution (its chemical equation is: 4HF+2LiMn2O4→3γ-MnO2+MnF2+2LiF+2H2O), cause the destruction of spinel structure, significantly speed up the decay of battery capacity, thus LiMn2O4The positive electrode of cladding is not suitable for using when high voltage, high temperature.
For another example, the U.S. Patent application of Application No. US20090309063, use LiM ' O2(M '=Co1-m-nNimMnn, 0.1 ＜ m+n ＜ 0.9, m >=n) and cladding LiCoO2, form " island shape " surface, to improve the cycle performance of material, high rate performance and high-temperature storage performance.LiM ' O is thought in this patent application2With LiCoO2In high-temperature sintering process, Ni, Mn, the Co in M ' can melt to LiCoO2Inside, LiCoO2In Co can melt to surface, formed " island shape " surface；But the shortcoming that this method has himself: first, M '=Co1-m-nNimMnn, as m ＞ n, LiM ' O2There is a small amount of Mn3+, and Mn3+Easily from positive electrode surface dissolution in cyclic process, and it is deposited on negative terminal surface, affects negative pole solid electrolyte (SEI) film, thus affect the cycle performance of battery；Second, technique is loaded down with trivial details, and Co is expensive, poisonous, and there is no need in clad to add Co, because matrix LiCoO2In Co can melt to surface, and there is the Co ion dissolution phenomenon from positive electrode surface in battery in cyclic process, and the Co of dissolution is deposited on negative terminal surface, affects negative pole SEI film equally；3rd, building-up process is readily incorporated SO4 2-Impurity, SO4 2-Battery performance can be had adverse effect on, capacity and the circulation of battery may be had influence on.
In view of this, a kind of surface configuration of necessary offer has the positive electrode of clad, what this clad had both had leads lithium ion, in the case of not affecting discharge platform, positive electrode can be used under higher charge cutoff voltage, thus improve the volume energy density of lithium ion battery, the positive electrode discharge capacity under high voltages height after cladding, cycle life can be made again excellent.Additionally, there is a need to provide a kind of lithium ion battery comprising this positive electrode, it had both had higher energy density, had again higher discharge capacity and excellent cycle performance.
Summary of the invention
An object of the present invention is: for the deficiencies in the prior art, a kind of surface configuration is provided to have the positive electrode of clad, what this clad had both had leads lithium ion, in the case of not affecting discharge platform, positive electrode can be used under higher charge cutoff voltage, thus improve the volume energy density of lithium ion battery, the positive electrode discharge capacity under high voltages height after cladding, cycle life can be made again excellent.Thus overcome positive electrode of the prior art to use structural instability under high charge cutoff voltage, even if or Stability Analysis of Structures, but the deficiency that cycle performance is the best, discharge capacity is the highest.
In order to achieve the above object, the present invention adopts the following technical scheme that a kind of anode material for lithium-ion batteries, described positive electrode is formed by body phase material and the skin-material being positioned at described body phase material surface are melted, so that body phase material and skin-material compact siro spinning technology, middle gapless, constant to ensure the compacted density of material, described body phase material is cobalt acid lithium, and the formula of described cobalt acid lithium is Li1+xCo1-yAyO2-zBz, wherein, 0≤x < 0.1,0 < y < 0.1,0≤z < 0.1, A is at least one element of Mn, Ni, Al, Mg, Ti and Zr, B is at least one of F, S and Cl, and described skin-material is the melted little granule of stratiform nickel ion doped composition, and the formula of layered nickel ion doped is Li1+mNi0.5-xMn0.5-yAzO2, wherein A is at least one of Al, Mg, Ti and Zr, 0≤m < 0.1,0≤x≤0.1,0≤y≤0.1,0≤z≤0.2, and it is 0.1 ~ 10% that described skin-material accounts for the mass percent of described positive electrode.
Wherein, stratiform nickel ion doped has the strongest structural stability and electrochemical stability under 4.5V, and therefore, the lithium ion battery of the positive electrode containing cladding stratiform nickel ion doped has good cycle performance under 4.5V.Preferably, the chemical formula of stratiform nickel ion doped is LiNi0.5Mn0.5O2, because LiNi0.5Mn0.5O2The valence state of middle Mn is+4 valencys, and there is not valence state is the+Mn of trivalent, thus inhibits the generation of Jahn-Teller effect.And LiNi0.5Mn0.5O2Reversible capacity at 3.0 ~ 4.5V has reached more than 180mAh/g, has good cycle performance under high voltages.
And, with LiNi0.5Mn0.5O2Cladding LiCoO2As a example by, in high-temperature sintering process, the surface of positive electrode can form Li1+xNi0.5Mn0.5CoyO2Solid solution.In this solid solution, the molar ratio of Ni Yu Mn be the valence state of 1:1, Ni be+divalent, the valence state of Mn is+4 valencys, thus greatly reduces the dissolution of Mn in cyclic process；And, this clad can also strengthen matrix LiCoO2Structural stability, reduce Co dissolution in cyclic process；Make the material discharge capacity under high voltages height after cladding, cycle life excellent.
Additionally, if the mass percent that described skin-material accounts for described positive electrode is too high, i.e. covering amount is too high, and the compacted density of material can be made to decrease, thus this mass percent should be less than 10%.
A kind of improvement as anode material for lithium-ion batteries of the present invention, it is 1 ~ 5% that described skin-material accounts for the mass percent of described positive electrode, this is preferred scope, to ensure that this positive electrode, while having higher compacted density, the most also has more stable structure.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, it is 3% that described skin-material accounts for the mass percent of described positive electrode, and this is preferably to select.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, described melted short grained median particle diameter D50It is 0.1 ~ 5 μm, to ensure that it plays higher discharge capacity and platform under high voltages.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the BET of described positive electrode is 0.1 ~ 0.9m2/ g, the median particle diameter D of described positive electrode50It is 8 ~ 25 μm.
Relative to prior art, the present invention has the following characteristics that owing to clad has excellent lithium ion conduction performance at the positive electrode of the Surface coating stratiform nickel ion doped formation of cobalt acid lithium, not only will not reduce the discharge voltage plateau of positive electrode, the discharge voltage plateau of this positive electrode can be improved the most to a certain extent；And this clad can also play effective gram volume under high voltages, strengthen the structural stability of matrix material, it is thus possible to significantly improve discharge capacity and the cycle life of positive electrode under high voltage.
Further object is that the preparation method that a kind of anode material for lithium-ion batteries is provided, comprise the following steps: the first step, soluble lithium salt, nickel salt, manganese salt, chelating agent and other inorganic salt are dissolved in solvent, forming mixed solution, other inorganic salt described is at least one in the magnesium salt of solubility, aluminium salt, titanium salt and zirconates.
Second step, the pH of the mixed solution of regulation first step gained is 6 ~ 8, pH now is partial neutral, the acid destruction to body phase cobalt acid lithium can be reduced, the most again body phase material is added in above-mentioned solution, stirring mixing, obtain solidliquid mixture, described body phase material is cobalt acid lithium, and the formula of described cobalt acid lithium is Li1+xCo1-yAyO2-zBz, wherein, 0≤x < 0.1,0 < y < 0.1,0≤z < 0.1, A is at least one element of Mn, Ni, Al, Mg, Ti and Zr, and B is at least one of F, S and Cl.
3rd step, the pH continuing the solution in regulation second step solidliquid mixture is 10 ~ 12, and now pH is alkalescence, it is possible to ensures that nickel manganese converts completely, and stirs mixing, is formed by the positive electrode of lithium nickel manganese composite oxide cladding.
4th step, the 3rd step is obtained by lithium nickel manganese composite oxide cladding positive electrode dry, roasting, formed stratiform nickel ion doped cladding anode material for lithium-ion batteries.
As a kind of improvement of the preparation method of anode material for lithium-ion batteries of the present invention, in the first step, described soluble lithium salt is at least one in lithium acetate, lithium nitrate or Lithium hydrate；Described soluble nickel salt is nickel acetate and/or nickel nitrate；Described soluble manganese salt is manganese acetate and/or manganese nitrate；Described solvent is at least one in water, ethanol and isopropanol；Described chelating agent is at least one in citric acid, tartaric acid and ammonia.
A kind of improvement as the preparation method of anode material for lithium-ion batteries of the present invention, in 4th step, positive electrode after first drying calcines 1 ~ 5h under the air atmosphere of 500 ~ 700 DEG C or oxygen atmosphere, then calcines 2 ~ 20h under the air atmosphere of 800 ~ 1000 DEG C or oxygen atmosphere.First tie at low temperature presintering, to form Li, Ni, Mn oxide, then carry out high temperature sintering, form perfect Li, Ni, Mn oxide stratiform crystalline phase.Wherein, it is contemplated that Mn calcining in oxygen can generate less Mn3+, thus preferably oxygen atmosphere carries out roasting to material.
This preparation method fully combines the advantage of liquid phase method and solid phase method, makes the surface of anode material for lithium-ion batteries be uniformly coated with by stratiform nickel ion doped, to form the anode material for lithium-ion batteries of melting structure；The compacted density of this positive electrode does not reduce, and use preparation method of the present invention to prepare the lithium ion battery of positive electrode discharge capacity under high voltages, cycle performance is all significantly increased.Additionally, this preparation method technique is simple, do not introduce impurity, it is easy to industrialization produces.
A kind of lithium ion battery of offer is provided, including positive plate, negative plate and the barrier film being arranged between described positive plate and described negative plate, and electrolyte, described positive plate includes plus plate current-collecting body and the positive electrode active material layer being arranged on described plus plate current-collecting body, described positive electrode active material layer includes that positive active material, conductive agent and bonding agent, described positive active material are anode material for lithium-ion batteries of the present invention.
As a kind of improvement of lithium ion battery of the present invention, described battery is 4.3V ~ 4.7V relative to the charge cutoff voltage of lithium.
Relative to prior art, lithium ion battery of the present invention is owing to employing the positive electrode that the present invention relates to, thus has the highest discharge capacity and excellent cycle performance under high voltages.And due to the raising of charge cutoff voltage so that this battery has higher volume energy density, it is possible to meet people's demand to lithium battery slimming.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings and detailed description of the invention, preparation method and technique effect thereof to the anode material for lithium-ion batteries of Surface coating stratiform nickel ion doped of the present invention are described in detail.
Fig. 1 is scanning electron microscope (SEM) figure of the positive electrode of the embodiment of the present invention 1.
Fig. 2 is scanning electron microscope (SEM) figure of the positive electrode of the embodiment of the present invention 2.
Fig. 3 is scanning electron microscope (SEM) figure of the positive electrode of the embodiment of the present invention 3.
Fig. 4 is scanning electron microscope (SEM) figure of the positive electrode of comparative example 1 of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.Wherein, covering amount refers to that skin-material accounts for the weight/mass percentage composition of positive electrode in each embodiment below.
Embodiment 1: the present embodiment provide positive electrode be covering amount be the Li of 3wt%1.01Co0.99Mg0.01O2/LiNi0.5Mn0.5O2Positive electrode, the BET of this positive electrode is 0.35m2/ g, D50=9.0μm.Wherein, Li1.01Co0.99Mg0.01O2/LiNi0.5Mn0.5O2Represent is with Li1.01Co0.99Mg0.01O2For body phase material, LiNi0.5Mn0.5O2For the positive electrode of skin-material, as follows.
Its preparation method is as follows: weighs the lithium acetate of certain mass, manganese acetate, nickel acetate and citric acid respectively and joins in 400mL water, and stirring is allowed to dissolve, and forms lithium nickel manganese mixed solution, and regulates pH value of solution=7.8；Add 250g body phase material Li1.01Co0.99Mg0.01O2Powder, stirs；Regulation pH value of solution=11.8, are uniformly mixed；After being dried by above-mentioned mixed solution, first roasting 2 hours under 600 DEG C of air atmospheres, then roasting 10 hours under 900 DEG C of air atmospheres, obtain the positive electrode of the present embodiment.
Embodiment 2: the present embodiment provide positive electrode be covering amount be the LiCo of 1wt%0.998Ti0.002O2/Li1.02Ni0.5Mn0.498Al0.002O2Positive electrode, the BET of this positive electrode is 0.27m2/ g, D50=15.0μm。
Its preparation method is as follows: weighs the lithium nitrate of certain mass, manganese nitrate, nickel nitrate, aluminum nitrate and ammonia respectively and joins in 300mL water, and stirring is allowed to dissolve, and forms lithium nickel manganese aluminum mixed solution, and regulates pH value of solution=6.2；Add 250gLiCo0.998Ti0.002O2Powder, stirs, and regulates pH value of solution=10.1, is uniformly mixed；After being dried by above-mentioned mixed solution, first roasting 4 hours under 550 DEG C of air atmospheres, then roasting 4 hours under 1000 DEG C of air atmospheres, obtain the positive electrode of the present embodiment.
Embodiment 3: the present embodiment provide positive electrode be covering amount be the LiCo of 8wt%0.99Ni0.01O2/LiNi0.5Mn0.45Zr0.05O2Positive electrode, the BET of this positive electrode is 0.22m2/ g, D50=18.0μm。
Its preparation method is as follows: weighs the Lithium hydrate of certain mass, manganese nitrate, nickel acetate, zirconium nitrate and tartaric acid respectively and joins in 400mL water, and stirring is allowed to dissolve, and forms lithium nickel manganese zirconium mixed solution, and regulates pH value of solution=6.7；Add 200gLiCo0.99Ni0.01O2Powder, stirs, and regulates pH value of solution=11.2, is uniformly mixed；After being dried by above-mentioned mixed solution, first roasting 5 hours under 700 DEG C of air atmospheres, then roasting 15 hours under 800 DEG C of air atmospheres, obtain the positive electrode of the present embodiment.
Embodiment 4: the present embodiment provide positive electrode be covering amount be the LiCo of 5wt%0.995Al0.005O1.95F0.05/LiNi0.49Mn0.49Mg0.02O2Positive electrode, the BET of this positive electrode is 0.19m2/ g, D50=22.0μm。
Its preparation method is as follows: weighs the lithium acetate of certain mass, manganese nitrate, nickel acetate, magnesium nitrate and ammonia respectively and joins in 400mL water, and stirring is allowed to dissolve, and forms lithium nickel manganese magnesium mixed solution, and regulates pH value of solution=6；Add 200gLiCo0.995Al0.005O1.95F0.05Powder, stirs, and regulates pH value of solution=10.6, is uniformly mixed；After being dried by above-mentioned mixed solution, first roasting 3 hours under 600 DEG C of air atmospheres, then roasting 10 hours under 950 DEG C of air atmospheres, obtain the positive electrode of the present embodiment.
Embodiment 5: the present embodiment provide positive electrode be covering amount be the Li of 10wt%1.01Co0.92Mg0.05Zr0.03O2/Li1.05Ni0.5Mn0.495Ti0.005O2Positive electrode, the BET of this positive electrode is 0.31m2/ g, D50=12.0μm。
Its preparation method is as follows: weigh in the mixed solvent (volume ratio of the two is 1:1) that the Lithium hydrate of certain mass, manganese acetate, nickel acetate, Titanium Nitrate and citric acid join 400mL water and ethanol respectively, stirring is allowed to dissolve, form lithium nickel manganese mixed solution, and regulate pH value of solution=7.5；Add 250g body phase material Li1.01Co0.92Mg0.05Zr0.03O2Powder, stirs；Regulation pH value of solution=11.3, are uniformly mixed；After being dried by above-mentioned mixed solution, first roasting 2 hours under 650 DEG C of oxygen atmospheres, then roasting 11 hours under 850 DEG C of air atmospheres, obtain the positive electrode of the present embodiment.
Embodiment 6: with the positive electrode Li of embodiment 11.01Co0.99Mg0.01O2/LiNi0.5Mn0.5O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Embodiment 7: with the positive electrode LiCo of embodiment 20.998Ti0.002O2/Li1.02Ni0.5Mn0.498Al0.002O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Embodiment 8: with the positive electrode LiCo of embodiment 30.99Ni0.01O2/LiNi0.5Mn0.45Zr0.05O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Embodiment 9；Positive electrode LiCo with embodiment 40.995Al0.005O1.95F0.05/LiNi0.49Mn0.49Mg0.02O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Embodiment 10: with the positive electrode Li of embodiment 51.01Co0.92Mg0.05Zr0.03O2/Li1.05Ni0.5Mn0.495Ti0.005O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Comparative example 1: with Li1.01Co0.99Mg0.01O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Comparative example 2: with LiCo0.998Ti0.002O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Comparative example 3: with LiCo0.99Ni0.01O2As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Comparative example 4: with LiCo0.995Al0.005O1.95F0.05As positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
Comparative example 5: with Al2O3The Li of cladding1.01Co0.99Mg0.01(it is abbreviated as Li1.01Co0.99Mg0.01-Al2O3, Al2O3Covering amount be 4wt%) as positive active material, after making slurry with bonding agent and conductive agent, it is coated on plus plate current-collecting body, make positive plate, negative plate is made as negative electrode active material using Delanium, positive plate, negative plate and barrier film are prepared lithium ion battery with common process, charge cutoff voltage be 4.4V(anodic potentials on the basis of Li as 4.5V), theoretical capacity is 1700mAh.
The lithium ion battery that embodiment 6 ~ 10, comparative example 1 ~ 5 prepare is assessed test as follows.
Discharge capacity test first: at 25 DEG C, with 0.5C(850mA) constant-current charge is to 4.4V, 0.05C(85mA) constant voltage to 4.4V, stand 5min, be then discharged to the capacity of 3.0V with 0.5C and be shown in Table 1 for discharge capacity first, acquired results.
Discharge voltage plateau is tested: at 25 DEG C, with 0.5C(850mA) constant-current charge is to 4.4V, 0.05C(85mA) constant voltage is to 4.4V, stand 5min, then it is discharged to 3.0V with 0.5C, test primary discharge capacity and discharge energy, discharge voltage plateau can be obtained: discharge voltage plateau=discharge energy/discharge capacity, acquired results is shown in Table 1.
Table 1: embodiment 6-10 and compare 1 to 5 the performance comparison of lithium ion battery.
Cycle performance is tested: at 25 DEG C, with 0.7C(1190mA) constant-current charge is to 4.4V, 0.05C(85mA) constant voltage is to 4.4V, then 1C(1700mA) it is discharged to 3.0V, 400 this charge and discharge cycles repeatedly, measure discharge capacity when discharge capacity when circulating for the first time and the 400th circulation, obtain the capability retention after circulation: the capability retention after circulation=(discharge capacity during the 400th circulation)/(discharge capacity during circulation for the first time) × 100%, acquired results is shown in Table 1.
As can be seen from Table 1, the contrast of embodiment 6 ~ 10 and comparative example 1 ~ 4 it appeared that: the lithium ion battery with the lithium cobaltate cathode material of Surface coating stratiform nickel ion doped as positive active material prepared by the present invention, discharge capacity and cycle performance under high voltage are remarkably improved, i.e. Li before cladding1.01Co0.99Mg0.01O2、LiCo0.998Ti0.002O2、LiCo0.99Ni0.01O2、LiCo0.995Al0.005O1.95F0.05And Li1.01Co0.92Mg0.05Zr0.03O2Discharge capacity first be respectively 1699mAh, 1696mAh, 1694mAh, 1692mAh and 1690mAh, the discharge capacity first after cladding is respectively 1707mAh, 1702mAh, 1698mAh, 1697mAh and 1695mAh；It is coated with under front 3.0 ~ 4.4V capability retention after 400 circulations and is respectively 60%, 63%, 65% and 65%, and the capability retention after being coated with is respectively 88%, 86%, 85%, 83% and 84%.These results show: after positive electrode cladding stratiform nickel ion doped, in the case of not affecting discharge voltage plateau, its discharge capacity under high voltages and cycle performance are significantly improved.This is because skin-material nickel ion doped has the lithium ion conduction performance of excellence, do not affect discharge voltage plateau, and effective gram volume can be played, improve the discharge capacity under high voltage；Skin-material nickel ion doped stabilizes the structural stability of body phase material simultaneously, improves the reversibility of removal lithium embedded under high voltage.
In addition, by embodiment 6 with the contrast of comparative example 1 and comparative example 5 it can be seen that although the positive electrode of conventional coated aluminum oxide can improve the cycle performance under high voltage, but its electric discharge gram volume and voltage platform can be significantly reduced, this is because aluminium oxide is non-electroactive materials, lead lithium ion very poor, thus the energy density of battery can be reduced to a certain extent.
Additionally, from relatively can be seen that of Fig. 1 to 3 and Fig. 4, the skin-material of the embodiment of the present invention 1 to 3 is rendered as melted little granule on the surface of body phase material, its D50 is about 2 μm, and body phase material and skin-material compact siro spinning technology, middle gapless, this shows: body phase material and skin-material define melting structure, constant to ensure the compacted density of material.
The announcement of book and teaching according to the above description, above-mentioned embodiment can also be changed and revise by those skilled in the art in the invention.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, should also be as some modifications and changes of the present invention falling in the scope of the claims of the present invention.Although additionally, employ some specific terms in this specification, but these terms are merely for convenience of description, the present invention is not constituted any restriction.
Claims (9)
1. an anode material for lithium-ion batteries, described positive electrode is formed by body phase material and the skin-material being positioned at described body phase material surface are melted, and described body phase material is cobalt acid lithium, and the formula of described cobalt acid lithium is Li1+xCo1-yAyO2-zBzWherein, 0≤x < 0.1,0 < y < 0.1,0≤z < 0.1, A is at least one element in Mn, Ni, Al, Mg, Ti and Zr, and B is at least one element in F, S and Cl, it is characterized in that: described skin-material is the melted little granule of stratiform nickel ion doped composition, and the formula of layered nickel ion doped is Li1+mNi0.5-xMn0.5-yAzO2, at least one element during wherein A is Al, Mg, Ti and Zr, 0≤m < 0.1,0≤x≤0.1,0≤y≤0.1,0 ＜ z≤0.2, it is 0.1 ~ 10% that described skin-material accounts for the mass percent of described positive electrode.
Anode material for lithium-ion batteries the most according to claim 1, it is characterised in that: it is 1 ~ 5% that described skin-material accounts for the mass percent of described positive electrode.
Anode material for lithium-ion batteries the most according to claim 2, it is characterised in that: it is 3% that described skin-material accounts for the mass percent of described positive electrode.
Anode material for lithium-ion batteries the most according to claim 1, it is characterised in that: described melted short grained median particle diameter D50 is 0.1 ~ 5 μm.
Anode material for lithium-ion batteries the most according to claim 1, it is characterised in that: the BET of described positive electrode is 0.1 ~ 0.9m/g, and the median particle diameter D50 of described positive electrode is 8 ~ 25 μm.
6. the preparation method of an anode material for lithium-ion batteries according to claim 1, it is characterised in that comprise the following steps:
The first step, is dissolved in soluble lithium salt, nickel salt, manganese salt, chelating agent and other inorganic salt in solvent, forms mixed solution, and other inorganic salt described is at least one in the magnesium salt of solubility, aluminium salt, titanium salt and zirconates；
Second step, after the pH of the mixed solution of regulation first step gained is 6 ~ 8, then adds body phase material in solution, and stirring mixing obtains solidliquid mixture, and described body phase material is cobalt acid lithium, and the formula of described cobalt acid lithium is Li1+xCo1-yAyO2-zBz, wherein, 0≤x < 0.1,0 < y < 0.1,0≤z < 0.1, A is at least one element in Mn, Ni, Al, Mg, Ti and Zr, and B is at least one element in F, S and Cl；
3rd step, the pH of the solution in the solidliquid mixture of regulation second step is 10 ~ 12, and stirs mixing, is formed by the positive electrode of lithium nickel manganese composite oxide cladding；
4th step, the positive electrode by lithium nickel manganese composite oxide cladding 3rd step obtained is dried, positive electrode after drying calcines 1 ~ 5h under the air atmosphere of 500 ~ 700 DEG C or oxygen atmosphere, then under the air atmosphere of 800 ~ 1000 DEG C or oxygen atmosphere, calcine 2 ~ 20h, form the anode material for lithium-ion batteries of stratiform nickel ion doped cladding.
The preparation method of anode material for lithium-ion batteries the most according to claim 6, it is characterised in that: in the first step, described soluble lithium salt is at least one in lithium acetate, lithium nitrate or Lithium hydrate；Described soluble nickel salt is nickel acetate and/or nickel nitrate；Described soluble manganese salt is manganese acetate and/or manganese nitrate；Described solvent is at least one in water, ethanol and isopropanol；Described chelating agent is at least one in citric acid, tartaric acid and ammonia.
8. a lithium ion battery, including positive plate, negative plate and the barrier film being arranged between described positive plate and described negative plate, and electrolyte, described positive plate includes plus plate current-collecting body and the positive electrode active material layer being arranged on described plus plate current-collecting body, described positive electrode active material layer includes positive active material, conductive agent and bonding agent, it is characterised in that: described positive active material is the anode material for lithium-ion batteries described in any one of claim 1 to 5.
Lithium ion battery the most according to claim 8, it is characterised in that: described battery is 4.3V ~ 4.7V relative to the charge cutoff voltage of lithium.
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103474663B (en) * | 2013-09-15 | 2018-01-23 | 东莞新能源科技有限公司 | Lithium ion battery, positive electrode and preparation method thereof |
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| CN108123114B (en) | 2016-11-28 | 2019-11-29 | 华为技术有限公司 | Lithium cobaltate cathode material and preparation method thereof and lithium ion secondary battery |
| CN106654169A (en) * | 2016-12-31 | 2017-05-10 | 山东精工电子科技有限公司 | Positive electrode plate of lithium ion battery and preparation method for positive electrode plate |
| CN106654224B (en) * | 2017-01-16 | 2019-11-29 | 湖南瑞翔新材料股份有限公司 | A kind of cobalt acid lithium composite material and preparation method, positive electrode |
| CN108134078A (en) * | 2017-12-13 | 2018-06-08 | 河南工业大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN110444817B (en) * | 2019-07-02 | 2024-04-26 | 萨姆蒂萨集成设备设计(邢台)有限公司 | Lithium battery |
| CN111261858A (en) * | 2020-01-21 | 2020-06-09 | 西安电子科技大学 | High-voltage lithium ion battery positive electrode material and preparation method thereof |
| CN112614990A (en) * | 2020-12-11 | 2021-04-06 | 格林美股份有限公司 | Nickel-manganese binary composite positive electrode material and preparation method thereof |
| CN112599859A (en) * | 2020-12-28 | 2021-04-02 | 长虹三杰新能源有限公司 | Preparation method of high-energy-density power battery |
| CN112736230B (en) * | 2020-12-30 | 2022-03-18 | 天目湖先进储能技术研究院有限公司 | High-voltage composite spinel-coated cathode material and preparation method thereof |
| CN112751006B (en) * | 2021-01-18 | 2022-04-15 | 北京大学深圳研究生院 | Cobalt-free lithium ion battery layered positive electrode material and preparation method and application thereof |
| CN113363440A (en) * | 2021-06-04 | 2021-09-07 | 昆山宝创新能源科技有限公司 | Positive electrode active material, preparation method thereof and battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102122712A (en) * | 2011-01-25 | 2011-07-13 | 宁波金和新材料股份有限公司 | Method for preparing high-compaction high-voltage lithium cobaltite cathode material |
| CN102394295A (en) * | 2011-11-23 | 2012-03-28 | 东莞新能源科技有限公司 | Lithium ion battery and its positive material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5153156B2 (en) * | 2007-02-13 | 2013-02-27 | 三洋電機株式会社 | Method for producing positive electrode for non-aqueous electrolyte secondary battery |
-
2012
- 2012-07-19 CN CN201210250864.XA patent/CN103137961B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102122712A (en) * | 2011-01-25 | 2011-07-13 | 宁波金和新材料股份有限公司 | Method for preparing high-compaction high-voltage lithium cobaltite cathode material |
| CN102394295A (en) * | 2011-11-23 | 2012-03-28 | 东莞新能源科技有限公司 | Lithium ion battery and its positive material |
Non-Patent Citations (1)
| Title |
|---|
| "锂离子电池正极材料Li-Ni-Mn-O体系的制备与改性研究";窦树梅;《中国博士学位论文全文数据库》;20111015;第C042-52页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3719886A4 (en) * | 2017-11-29 | 2021-08-04 | XTC New Energy Materials(xiamen) Ltd. | Lithium ion battery cathode material, preparation method therefor, and lithium ion battery |
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